DE1568717A1 - Process for making polyether diols using water as telogen - Google Patents

Description

Process for making polyether diols using water as telogen

The present invention relates to a method for Her = represent polyoxyalkylenediols with terminal hydroxyl groups and in particular a process for preparing liquid polyoxyalkylene diols.

An object of the present invention is a method for producing polyoxyalkylene diols, their hydroxyl groups are essentially terminal.

Another object of this invention is a method for Production of relatively low molecular weight, liquid polyoxyalkylene diols with a hydroxyl functionality of about 2.

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Documents (Art. 7 & I Abu. 2 No. I sentence 3 de "Amendment notices" .

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These and other objects and advantages of the present invention will become apparent to those skilled in the art from the following Take the description and the examples »

It has now been found that polyoxyalkylene diols, their Hydroxyl groups are practically terminal, can be produced if you (1) epoxy and / or oxetane monomers with (2), water (3) polymerized in the presence of certain double metal cyanide complexes, which have been treated with organic substances such as alcohols, ethers, esters and the like. Depending on the The amount of water used can be the polymers obtained (hereinafter referred to as telomeres) from Ltientölen to su Petten and solids with a hydroxyl functionality vary from about 2.

Organic cyclic oxides, which according to the invention Procedures that can be telomerized are for example oyolisoht oxides such as 1,2-epoxides, oxetanes, 3-eubet.-oxetanes or 3 »3-disubstituted oxetanes with an oxygen-carbon ring, in which one oxygen atom with 2 or 3 ring carbon atoms linked 1st, which after opening the ring with the same or other cyclic oxide monomers in the presence telomerize the Boppelmetalloyanidkomplex catalyst

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and which contain up to a total of 18 carbon atoms, the means 3 carbon atoms in the ring and up to 15 carbon atoms atoms in the side chain ^ These cyclic oxide monomers can also contain 1, 2 or more aliphatic double bonds. The cyclic oxides preferably contain only one aliphatic carbon-carbon double bond. Also the alkenyl *, ether- and halogen-substituted derivatives (with the exception of easily ionizable halogen) of these cyclic oxides can be used

Examples of suitable cyclic oxides, which according to the Invention "The method may be used on _9: Äthylenoxyd- (1 ₉ 2-Ep oxyäthan), 1,2 'propylene oxide oxide ₉ 1' 2 ~ ~ butene, 1,2-Hexenoxyd _¥ 1,2-dodecane monoxide, isobutylene oxide, styrene oxide, 1 »2-pentene oxide, isopentene oxide, 1,2-heptene oxide, allyl glycidyl ether, isoheptene oxide, 1» 2-octene oxide, methyl glycidyl ether, ether, ether oxide, isopentylene oxide, phenyl ether oxide, 3-propylene oxide), tolyl glycidyl ^{ether, 3 ~ 3 m} dimethyloxetane »3-allyl-3-» ethyloxetane, 3 ~ vinyl-3-iietbyloxetane, 1,2-pentadecenoxide, 3-butyl-3-decyl-oxetane, 3-chloromethylene oxetane, 3- Chlomethyl-3-methyloxetane and the like.

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It is preferred to use low molecular weight oxides, such as Äthylenoxydet propylene oxides, butylene oxides and the like, containing 2 to 12 carbon atoms.

The double metal cyanide complex catalysts suitable for the process according to the invention are produced indene a transition metal cyanide complex with a Metallealz is reacted in an aqueous medium. The removal of practically all of the water present in the catalyst is desirable, to increase the effectiveness of the catalyst * although it appears that removing all water does not feasible and possibly also not desired. It has been found that most of the water is removed and the The effectiveness of the catalyst can be further increased if the catalyst is used with a complexing or coordinating agent Substance such as an alcohol, ether, ester, sulfide, ketone or aldehyde is treated.

In general, the double metal cyanide catalysts used according to the invention have the following constitutional forms

where N denotes a metal ion, since «a Me t * 11 acid · t off-

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Forms bond that is relatively more stable than the coordinative bond between the metal and the nitrogen * atom of the cyano group, CN. M *, on the other hand, means a transition metal ion that forms more than one stable valence stage and forms a relatively firm, covalent bond with the carbon atom of the cyano group _e A one of its catalysts can have more than one type of M- or M'-metal ion in its structure. With the oyanide ion, which shares in the electrons of the two metal ions, these metals usually form the following polymeric structure: (-M'-CN ... M ... NC-M ¹ ) _n »where η is an integer and at least 1 and, depending on the coordination numbers of M and M *, super-three-dimensional polymers can be formed. In addition, these metal ions, which form active cyanide catalysts, can all enter into coordinate bonds with 6 groups (sum example as in hexacyanoferrate- (III)). Most hexacyanoferrate- (III), such as zinc hexacyanoferrate- (III), have a cubic, surface-centered lattice.

The CN 'group forms the bridge in the catalyst molecule. However, there can also be other bridge groups in the Catalyst molecules must be present, provided that the majority of the bridges in the catalyst molecule have CUT groups

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are. So r and t are numbers, where r is greater than t. t is only 0 if the CH group forms the bridge. For example, X, which can be present in addition to the CH ~~ group in the above formula, F ", Cl", Br ", I", OH * "» HO, 0.00, H ₂ O, HO ₂ , C ₂ OT "or other acid residues such as SOT", OHS ", CHO", NCO ", HCS" and the like mean.

In the formulas given above, M preferably denotes a metal from the group Zn (II), Fe (II), Fe (III), Co (II), Hi (II), Mo (IV), Mo (VI), Al ( III), V (IV), V (V), Sr (II), W (IY), W (VI), Mn (II) and Cr (III). On the other hand, M 'is preferably a metal from the group Fe (II), Fe (III), Oo (II), Co (III), Or (II), Or (III), Mn (II), Mn ( III), V (IV) and V (V). A, b and c are also integers whose values are functions of the valences and coordination numbers of M and M ¹ . The total net positive charge on M multiplied by a should be practically equal to the total net negative charge on M ¹ I (0 H) _b | or

multiplied by o, be. In the mei-

In most cases, b corresponds to the coordination number of M 'and is usually 6.

Catalysts which can be used for the method according to the invention

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Ren, which fall under the definition given above, are for example zinc hexacyanoferrate- (III), Zinkhexacyanoferrat- (H) ₈ nickel- (II) -hexacyanoferrat «(II), Nickel- (II)» hexacyanoferrat- (III) * Zinc hexacyanoferrate (III) hydrate, cobalt (II) hexacyanoferrate (II), nickel (II) hexacyano s errate (III) hydrate, iron (II) hexacyanoferrate (ΓΙΙ), cobalt - (II) -hexaeyanoa obaltat- (HI) ₉ zinc hexacyanoo obaltate »(II), zinc hexacyanomanganate- (H) ₆ zinc hexacyanochromate- (III), zinc iodpentac.yanoferrate- (III) _g cobalt- (II) ~ chloropentacyanoferrate- (II), cobalt «(II) -brompentacyanoferrate- (II), iron- (II) = fluoropentacyanoferrate- (III) $ zinc chlorobrometracyanoferrate- (III), iron = (III) -hexacyanoferrate- (III), aluminum dichlorotetraeyanoferrate- (III), Molybdenum- (IV) -brom- pentacyanoferrat- (III) ₉ Molybdenum- (VI) -calorpentacyanoferrat- (II) _f Vanadium- (IV) -hexacyanoehronat- (II) »Vanadium- (V) -hexacyanoferrate- (XIII), strontium (II) hexacyanomanganate (III), tungsten (IV) hexacyanovanadate (IV), aluminum chloride acyanovanadate- (V), tungsten- (VI) -hexaoyanoferrate- (III), manganese (II) -hexacyanoferrate- (II), chromium- (III) -hexacyanoferrate- (III) and the like I Pe (CN) ^ 10 J ι ZJT (CN) IKD Znpe (ON) ₅ OoI, Zn [Fe (CH) H

^ Ö71 p ^i>

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, Ni ₃ J ^ (CN) ₅ CNs] ₂ and the like. Mixtures of the above compounds can also be used «

In general, the complex catalysts of this invention are prepared by adding aqueous solutions of salts which form a precipitate of a metal salt from a transition metal _{complex anion, for example by the reaction M a} Q + Μ "Γμ» (Υ) 3 ₀ -> ^M J "# ¹ BJC ^ ^{+ M} "Q> brings ^the implementation, where M is a metal ion precipitates _(the Komplexanionsalze; for example, Zn ^++, means In the above equation, a, b and β are integers;. have but not necessarily on both sides of Equation has the same value as they are punctures of valences and coordination numbers of M, M ', M "and possibly Y and Q. Q is a halide or other anion, for example Cl""M" is a hydrogen or a metal ion , whose complex anion salts are "soluble" in water or another solvent, for example K ⁺ , Ca ⁺⁺ and the like. M * is a complex-forming transition metal ion, for example Fe ⁺⁺⁺ o Y is a complex-forming anion, for example CN "ο In preparing the complex yanide catalysts useful for the present invention, an excess of Mo is usually

El.

wishes.

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Foreign ions contained in the solution used for the preparation of the precipitate are apparently easily included in the complex precipitate. Anions (Cl "and so on) are assigned to the positively charged metal ions in the lattice, and cations (K * ¹ *) are coordinated to the negatively charged nitrogen atoms of the cyanide bridging groups. These ions, especially those anions that coordinate with the Connect M atoms, inhibit the catalytic effectiveness or prevent the complex from causing a noticeable polymerization. In addition, these ions, such as easily ionizable Cl, can break the polymer chain.

In order to obtain a catalyst that has the highest effectiveness for telomerization, one sets the catalyst precipitate, an organic complexing agent is preferably added before it is centrifuged or filtered. This complexing agent can be mixed with the water when washing the precipitate · It can be used alone! · washing medium can be used, provided that the Complexing agents can replace the trapped ions or dissolve, or it can be used for treatment or to wash off the precipitate after this with water

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has been washed, used to replace at least a part of the water. So that the effectiveness of the Catalyst is improved, a sufficient amount of complexing agent must be used for this. Such a complex-forming agent should, if possible, with the M element or -Ion enter into a coordination bond and should be an organic compound with a relatively low molecular weight · It should preferably be miscible with water or soluble therein or at least practically soluble and essentially straight-chain; it can contain up to 18 carbon atoms, hold · Preferably the complexing agent contains only up to 10 carbon atoms and is one at room temperature Liquid.

Complexing agents which can be used in the double metal cyanide catalysts are, for example: alcohols, aldehydes, Ketones, monoethers, dieters, polyethers and acyclic, aliphatic Polyether. Examples of the alcohols are: methanol, ethanol, propanol, isopropanol, butanol, octanol, Ootadecanol and the like. Examples of the aldehydes are: formaldehyde, acetaldehyde, butyraldehyde, valerianaldehyde, Glyoxal, benzaldehyde, toluene aldehyde and the like. Examples for the ketones are: acetone, methyl ethyl ketone, 3-pentanone,

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2-hexanone and the like. Examples of the cyclic ethers are: dioxane, trioxymethylene and paraldehyde. Aliphatic, saturated monoethers, dieters, foly ethers and acyclic, aliphatic polyethers are also suitable as treatment agents; such ethers are, for example: diethyl ether, 1 ~ ethoxypentane, bis- (ß-chloroethyl) - = ether _t butyl ether, ethyl propyl ether, bi8- (ß-methoxyethyl) ether, ethylene glycol, di-ethyl ether, triethylene glycol, methyl ether, methyl ether, methyl ethoxymethlycol, octylene glycol, methyl ethoxymethane, methyl ethoxymethyl ether, methyl ether , Dimethyl ether and the like. The acyclic Folyäther are preferred * Other useful complexing agents include: amides _t esters, nitrites and sulfides, such as formamide, acetamide, propionamide, butyramide, valeramide, amyl formate, ethyl formate, hexyl formate, propyl · * formate, methyl acetate, ethyl acetate, Propylmcetat , Triethylene glycol diacetate and the like; Acetonitrile, propionitrile, and the like "; dimethyl sulfide, diethyl sulfide, dibutyl sulfide, biamyl sulfide, and the like. Ethers having more than one oxygen atom that chelate with metal M are preferred. Mixtures of these organic complexing agents can be used If a larger amount is present than is necessary for complex formation with the metal catalyst, the excess

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shot can be removed by extraction with a hydrocarbon solvent such as pentane, hexane and the like.

After treatment with the organic complexing agent, the catalysts have the following constitutional formulas:

M ¹ CCW) J ₀ , (H ₂ 0) _d . (R) ₆ and / or

'< ^H 2 °> d ^(R) e *

where d is an integer or a fraction and e is an integer or a fractional number, since the catalyst is a non-stoichiometric complex in which "different amounts of water can be present and the R groups can be bound to the various metals" e means bull when the catalyst is not treated with the complexing agent. R is one or more of the complexing agents such as the organic amides, alcohols, aldehydes, esters, ethers and the like given above. M, M ', CH, X, a, b, c, r and t have the same meanings as above. In general, the values of d and e correspond to the coordination number of H. Both HgO and R know to be included in the crystal lattice. In general, dl "Suaae der Oxygen-" ¹ nitrogen and / or sulfur atoms or other coordinating atoms of H ₂ O and R (depending on the organic "complexing agent) is at most about 0 * 1 to about 5 * 0 gAtom per gAtom des , Metalls M.

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VNSPECTED

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Since the catalyst is then heated and removed of the water and / or the organic complexing agents is dried, the catalytic effectiveness of the product obtained has been completely or practically completely lost »

As shown in the formulas above, when the organic complexing material is not used, R is absent so that e is zero. Thus, the same formula for these catalysts is Ma (Z) ₀ . (H ₂ 0) _d . (R) _e , where M, H ₂ O, R, c, d and e have the meanings given above, d and e can also be equal to zero or approach zero. Z means the groups M ¹ (CN) _b or M ^l ^ rCN) _r (X) _ta> 7 _b . M ¹ , CN-X, b, r and t have the meanings given above. “In the above formulas, the indices represent whole numbers or fractional numbers.

When preparing the catalyst it should be noted that the catalyst, if it is filtered off or centrifuged off from the solution in which it was made, and then bit one of the polymerizable cyclic oxides, such as propylene » oxide that is washed, little or no catalytic see effectiveness shows »To a storage-stable catalyst

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For the polymerization of such cyclic oxides, the catalyst should be obtained from the solution in which it is made was, filtered off or centrifuged and then with water and an ether or some other organic, complex-forming Compound of the type described above and then washed with one of the cyclic oxide monomers. This makes EU a very effective type of catalyst.

After the washing steps, the catalyst can be used as such. However, it is preferably dried in order to remove excess treating agent and any easily removable residual water and in order to obtain a material which is easier to handle. Such drying is effected by means of a vacuum or by heating dea Kataly = crystallizer in air or an inert atmosphere to a temperature Ton about 100 ⁰ C. Preferably, the catalyst in vacuo at low temperature (for example at 0.5 to 1 mm and 25 Bg ⁰ C) or dried in a stream of air, nitrogen or inert gas at 5 to 25 ^{° C.} A catalyst treated in the heat shows a lower efficiency and must therefore be used in a higher concentration than a catalyst treated in a vacuum. High temperatures must be avoided because the drying temperature is increased

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the effectiveness of the catalyst decreases. It is assumed that at then high temperatures part of the oxygen-containing agent or of another organic complex-forming agent whose coordinative bond to the metal M is weak can be lost, so that vacancies remain in the crystal lattice and the atoms in the crystal lattice sioh to the satisfaction of can rearrange the coordination required by the metals3. Heating can also lead to the removal of gyanide ions and reduce the metal M '. It is also possible that the molecular weight of the catalyst can increase, as a result of which the number of metal ions exposed on the catalyst surface and / or the active sites is reduced. Freshly prepared catalysts are preferably used; since the catalysts slowly decompose during storage and so the catalytic efficiency is reduced. When the catalysts extended period of time should be kept, it stores them preferably down "set temperatures _t to reduce the decomposition.

Although it is not exactly known to which gears the usefulness of the double metal cyanide complexes in this polymerization is due, it can be assumed that a the following processes are responsible for it. Even though

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Before the discussion below deals with the treatment of double metal alloy catalysts with ethers, it is easy to see that it is also generally applicable to treatment with other organic complexing agents of the type described above. As was explained using zinc hexaoyanoferrate, for example, “a more effective catalyst is produced when the precipitate is washed with dioxane. During this treatment with dioxane, a large number of reactions presumably take place (1) A rope of the chloride ions in the lattice is oxidized, which leads to the reduction of Pe (ZII) cu Pe (II); (2) the chlorine from reaction (1) reacts with water and ether present during the washing treatment; Cl "and chlorinated ether are formed; (3) the subsequent washing steps remove some of the products of the reaction (2 \ and (4) the oxygen atoms of the ether obviously enter into a coordination bond with the zinc ions in the lattice, the lattice structure being caused by the insertion is rearranged by dioxane groups between the zinc ions as follows: r-CHgC ^ -j

-Pe-CK ... Zn ... 0-CH ₂ GH ₂ -O ... Zn. · .NC-Pe-

So resulted in some dioxane-zinc hexacyanoferrate complexes in the pail the elemental analysis that these complexes were apparently not stoichiometric and corresponded to the following formula:

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₂ (C ₄ H ₈ Og) _x (HgO),. where y «1 to 2 and χ a 2.5 bia 3» 1, according to the IR and elemental analysis, part of the dioxane in the complex can be chlorinated and part of the HgO in the form of = OH or ~ O = groups . If prepared as usual, these complexes generally contained about 4 to 5 $> Cl "and a smaller amount of K ⁺ ,

If the catalyst is made with Zn (NO-) g instead of ZnClg will be about 50 # the normal amount of dioxane built into the catalytic converter. This catalyst is not as effective as the one made from the chloride »

Although there is a large rope of iron in the ether (or another organic complex-forming component) -zinc hexacyanoferrate complex, presumably as a result of the oxidation-reduction reaction that takes place during production, that of ZnGl ₂ and K ₄ Pe ( CLJ) ₆ the dioxane produced not as effective, even at a polymerization temperature of 8O ⁰ C. The analysis showed that a lower amount of dioxane was incorporated in such a complex and that the chlorine content was high *

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The reduced catalytic effect when using Zn (NO ^) ₂ or K ^ Fe (CN) ₆ in the production of the catalyst complex is probably related to the mechanism of the ether-hexaeyanoferrate reaction. This mechanism can be considered as follows: Since the chloride ions of the surface zinc ions in the crystal lattice donate electrons to the Zn ».. NC-Fe group, ether molecules can displace the sieve-forming chlorine atoms and form ether-zinc coordination bonds. For example, the following reaction takes place from »Zn ₃ [Fe (CN) ^] ₂ (KCl) + yROR ^ Zn ₃ KyITe (CN) I ₂ -

(ROR) + yCl °. (Note that y in the above = y

equation is a number and does not need to have the same meaning as * u in the earlier formulas). The driving force for these reactions is the removal of the Cl ₂ by dissolving the gas in the water and ither and the reaction of the Cl ₂ with the ether »

This oxidation-reduction reaction and displacement of the chlorine by ether is accompanied by a change in the crystal lattice, according to the elemental and infrared analysis, most of the zinc ions in the lattice seem to form coordination bonds with 1 to 2 oxygen atoms. Both the oxygen atoms and water are in this coordination bond

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as well as those of the aether. X-ray analysis and density measurements seemed to confirm this lattice change. So the oxygen atoms of the ether compete with the CN groups dee Fe (ONj ^ -Anions in the formation of a polymer structure with more exposed zinc ions, as shown below.

“CN

H-O. H

Zn

N
C.

OC ₄ H ₈ O .0C ₄ H ₈ O

This process of opening the grid is promoted by the presence of water during the ether treatment «Apparently the water dissolves the Pe (CN) g anion = sections of the grid» which ^{are coordinated with K +} ions »so that a larger part of the Lattice is exposed to the ether during the hexacyanoferrate ether reaction _o

I) Ie experiments have shown that chloride ions in the double metal · = nyantdkomplex catalyst the polymerization of the cyclic

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Can inhibit oxides. So let us wish the crowd of ionizable chlorine and other ionizable anions in Reduce catalyst. For example, the catalyst bit can be washed in an ether-water solution, whereby the soluble chloride salt can be removed · Zinc hexaeyanoferrate is produced using a different method by converting compounds such as calcium iron III cyanide, Aluminum iron III cyanide or lithium iron XII cyanide, with zinc chloride, and the calibrating chloride salt can get through the ether during the washing process removed. It was also found that ions, such as Cl ", which are covalently bound to the complex-forming catalyst, apparently cause the polymerization of the epoxies and oxetanes do not affect adversely · It was even shown that chlorinated ethers improve the effectiveness of the catalyst, as presumably halogenated Xther to initiate the polymerisation are more easily displaced by the epoxies and oxetanes.

The polyethylene glycol ethers are preferably used for the treatment of the Soppelmetalloyanids, since a very effective catalyst is obtained. Apparently one forms Ohelate bond with the zinc ion, creating the driving force

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the hexacyanoferrate = * ether "response is amplified and a very open lattice structure forms _t since the polymeric coordination is prevented via the Säueretoffatom. It has been found that "the use of dimethyl or diethyl ethers of ethylene glycol increases the effectiveness of the catalyst". It thus appears that the most effective catalysts for the polymerization of cyclic oxides are those which have the most zinc = "Saueret off" ether " = Bin = fertilize (instead of zinc-oxygen-water bonds) and have at least ionizable chlorine atoms «

You applied catalyst amount can from about 0.001 to 15 percent by weight, based on the total weight of the during telomerizable, cyclic ones used in telomerization Oxide monomers, range. It is preferable to use around 0 * 01 up to 1.0 percent by weight of catalyst, based on the total weight of the monomers.

You amount of water that is used as telogen in the inventive The method used depends on the molecular weight of the desired polyoxyalkylenediol. You amount of water can vary from 0.0001 percent by weight to 5 * 0 percent by weight, based on the polymerizable oxide.

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If molecular weights below 5000 are desired, the amount of water should be about 0.4 # and above. This Water is added to the propylene oxide and does not include any water that may be included in the catalyst · The cyclic oxide can be in bulk or in a solvent To be telomerized · It should be under inert or non-oxidizing conditions, for example under nitrogen, argon, necn, helium, krypton or another Inert gas, to be telomerized. Ss can also be telomerized under the pressure of the vaporized cyclic oxide.

When large amounts of water are used to create low molecular weight telomeres, the water becomes advantageously added in proportions, since large amounts of water reduce the rate of selomerization »Da» with a reaction rate that is acceptable for practical needs is thus obtained, the addition of the takes place Water in proportions. This method can also be used for the preparation of telomeres with a broader molecular weight distribution than is achievable if that all water is added immediately at the beginning of the reaction.

Telomerization we! preferably in a closed one Container at atmospheric pressure or slightly above

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carried out at atmospheric pressure. The pressure should be sufficient to disperse the catalyst and the heat transfer to maintain a liquid state "It is, however, also possible" for telomerization to obtain gaseous, monomeric, cyclic oxides in the solution to be leveled.

The temperature at which the process according to the invention is carried out, iei; not critical and can vary from about 0 to 12 ° C. or about »above. An induction period is preferably who "the temperatures of about 15 to 80 ⁰ G applied in some instances observed with the less active catalyst species ·

The telomerized which can be obtained by the process according to the invention Product can generally be obtained by using organic diisocyanates such as toluene diisocyanate, p-phenylene diisocyanate, Ethylene diisocyanate, trimethylene diisocyanate, dodecamethylene diisocyanate, Butylene-1,2-diisocyanate, m-phenylene diisocyanate, Benzene-1,2,4-triisocyanate, polyethylene polyphenyl isocyanate and the like, eur production of polyurethane foams and elastomers are stretched. You polyurethane elastomers are used as sealing rings, floor mats, Schuhabs & tae »

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Motor holding oranges and the like are suitable. The polyurethane = Foams are useful for insulation and the like

The following examples are intended to further illustrate, but not limit, the invention. In the examples are all ropes »unless expressly stated otherwise, parts by weight.

example 1

A zinc hexacyanoferrate dioxane complex catalyst (essentially Ζη, (ϊβ (0Η) _ό ) _2. 3.1 CLHgO ₂ · 1.6 H ₂ O) was prepared as follows: 200 μl of an aqueous solution of K-Pe (CN) ₆ (0.430 molar) were slowly added to 75 μl of an aqueous solution of zinc chloride (1.89 ttolar). This corresponds to an excess of 10 mol? C zinc chloride. The precipitated zinc hexaoyanoferrate was centrifuged off (2000 revolutions per minute for 50 minutes) and washed 4 times with 200 BI portions of anhydrous, peroxide-free dioxane and ^{dried at 25 0} O under a pressure of less than 1 mm Hg overnight. It was used to catalyze the polymerization of propylene oxide and allyl glycidyl ether in the presence and in the absence of water. 0.1 g of the zinc hexaoyanoferrate dioxane complex and 0.1 g of phenyl - / ^ - naphthyl-

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The amine and air were poured into a dry beverage bottle that was closed with a crown and contained a stirring stick. The bottle was flushed with nitrogen, sealed and charged with 47.1 g (0.81 mol) of propylene oxide and 2.88 g (0.25 mol) of allyl glycidyl ether by means of an injection syringe. In the first pail the propylene oxide contained no water, and in the second it contained 0.00023% by weight of water. They polymer obtained at the same conversion level (93 £) showed intrinsic Yiscositaten in iso propanol at ~ 6O ⁰ C of 4.9 and 2.8. This shows the molecular weight lowering effect of water.

B β is ρ 1 e 1 2

In this example, a zinc hexacyanocobaltate-aoetone complex prepared as follows was used as the catalyst: A solution containing 694 β CaJco (NO ₂ and 505 g water was added dropwise to a solution of 55.5 g ZnCl ₂ in 63.2 g water . was added 1895 g of acetone to the slurry of the precipitate in water, and the mixture was stirred for 15 minutes the precipitate abzentrifuglert (7000 rpm, 40 minutes) and then ten times with 70 VoI ₀ -. washed * Aoeton in water door every

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Wash used approximately 2000 ml of solution. After two further washes with 2000 ml of pure acetone, the solid cake ^{was dried at 25 °} C. under a pressure of less than 20 mm Hg for 9 to 10 hours.

The general procedure for the telomerism atlon reaction is the following The catalyst was placed in a dry beverage bottle The bottle was sealed, evacuated and filled with nitrogen. 2 g of a propylene oxide-water mixture were added by means of a hypodermic syringe · The bottle was then placed in a bath »the was held at a constant temperature of 80 ° 0 and agitated in an overhead rotating arrangement. the Appropriate values are compiled in Table I. The molecular weight was determined by vapor phase osmometry certainly. The hydroxyl content was determined and the functionality was calculated in such a way that the number of Get hydroxyl groups by dividing the number of moles of the telomer

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I e. b e 1 1 e I

Water in Kats.lysa- time in $> Aue- * Molecu- function-

suohe PO Gew. ^ tor Gew. 9 & hours booty large w. nail tat

A 0 _p 18 0 _s 02 2.5 92 8500 1.9

B 0.36 0 _f 04 24 92 4000 2.1

C 0.54 0.16 22 70 2150 2.2

D 0.72 0.16 24 81 1450 2.3

Example 3

The catalyst used in this example was like is made as follows:

A glyme-zinc hexacyarocobaltate complex (essentially Zn- | co (CN) ₆ | ₂ · 1.7 glyme. 1,2 H ₂ O .1,2 ZnCl ₂ ) was prepared as follows: 100 ml of an aqueous solution of K. ₅ Co (CN) ₆ (0.296 molar) were passed through a bed which contained Amberlyst 15 in the acid form. In this procedure, H ^{+ was} exchanged for K ⁺ . The acidic solution was then concentrated to a volume of 80 ml at room temperature, which gave a 0.370 molar solution of H-Co (CN) _6. The solution was then rapidly mixed with 10 ml of an aqueous solution of ZnCl. (4 «87 molar) mixed. This corresponds to a surplus of 10 Ko! £ ZnCIg. After complete precipitation of

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ZnJOo (CN) ₆ L was slowly added 60 g of glyme to the aqueous slurry and the mixture was stirred for 15 minutes. The precipitate was centrifuged off (7000 revolutions per minute, for 40 minutes) and then washed twice with glyme (total volume: 188 ml). The precipitate was isolated and scbliesslioh at 25 ⁰ C under a pressure of less than 1 mm Hg dried overnight "glyme is the Dinethylather of ethylene glycol.

0.08 g each of the catalyst - (Zn, Co (CN) ₆ I ₂ · glyme (0 ₉ 08 g) - were weighed and placed in 338 g Pyrex bottles. All bottles were washed and rinsed in deionized water and added to 200 ° C. After filling the catalyst, the bottles were immediately closed and evacuated to a pressure of less than 22 mm Hg for 15 minutes a syringe added the vials were immediately placed in a safety container and hot in a 80 ⁰ C bath placed in reeling motion. the appropriate values of this example are summarized in the following table.

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BATH

009818/176 9

9923-B

tab Catalyst, g Hurry II B. C. D. Propylene oxide, g A. 0.08 0.08 0.08 Ml water
1 »encore 0.08 50 50 50 2 ο addition 50 0.35 0.20 0.20 all in all 1.00 0.65 0.80 0.80 Time between the
1 »and 2nd addition of water ^^ 1.00 1.00 1.00 Response time, hours 1.00 218 min 100 Hin 68 min Temperature » ⁰ C 24 24 24 io conversion 24 80 80 80 Hydroxyl number 80 22.6 52.5 40 ₉ 8 6.3 261 58.1 76.9

From the above waiting it can be seen that through the an « partial addition of water reduces the yield of the telomer is greatly improved °

BATH ORIGINAL

»29 -

00 9 818/1769

Claims (8)

The General Tire and Rubber Company 992> B (Q 48194) Claims Process for the production of polyoxyalkylene ether diols, in which the hydroxyl groups are essentially at the end, characterized in that there is at least one polymerizable, organic, aromatic cyclic oxide, which has a ring of 2 to 5 carbon atoms and one oxygen atom and up to a total of 18 carbon atoms contains, from the group epoxides, oxetanes, 3-eubst. -oxetanes and 3, ^ - dlsubst "-Oxetane with about 0.0001 to 5.0 wt%. 'Water, based on the polymerizable oxide, in the presence of about 0.001 to 15% by weight of a catalyst, based on the polymerizable oxide, mixed, the catalyst being a double metal loyanide complex compound of the general formula M _ft (Z) _0. ( HgO) ^ (R) ₆ , where Z M * (CN) _b or M ¹ (CN) _r (X) _{t b>} M contains at least one metal from the group Zn (II), Pe (II), Pe (III), Co (II), Nl (II), Mo (IV), Mo (VI), Al (III), V [IV), V (V), Sr (Il), W (IV), W (VI), Mn (II) and Cr (HI), M * a metal from the group Pe (II), Pe (III), Co (II), Co (III), Mn (II), Mn (III), Cr (H ), Cr (III), V (IV), and V (V), XP ~, Cl ", Br", Γ, OH ^- , NO, 0 "", CO, HgO, C ₂ O ^ "" *, 30 ^ "% CNO", CNS ", NCO ^- or NCS", R is a low molecular weight organic compound with up to 18 carbon atoms from the group alcohols, aldehydes, ketones, Xethers, esters and amides, nitriles and sulfides, a, b and 0 Numbers whose values are punctures of the valences and coordination numbers of M and M ⁴ , with the entire BAD N§U9 fWMyW frfrlflAS XdWi 9923-B positive «net charge of H times a practically equal to the total negative net charge of Z times ο« r is an integer »t an integer ZaM ₀ where r is greater than t 1st« d means zero or an integer and e means zero or an integer "And that the mixture is kept at a temperature" at which the water and the cyclic oxide react with one another to form polyoxyalkylene ether oils. 2. The method according to claim 1 »characterized» in that the temperature is approximately 0 to 180 ^° C. 5. The method according to claim 1, characterized in that the temperature is 15 to 80 ^° C. 4. The method according to claim 5, characterized in »that the polymerization is carried out in the presence of a solvent for the monomer. 5 »The method according to claim 2» characterized «that the catalyst in an amount of about 0.01 to 1 Qew.ji and the water in an amount of 0.001 to 1 wt used. 6. The method according to claim 5 »characterized» that the catalyst is a zinc cotoaltioyanide ketone complex. 7 · The method according to claim 5 * characterized in »that the catalyst a zinc-ocbaltioyantd-oyclodiäther-Köra » lex 1st. 8. The method according to claim 5, characterized in »that the catalyst is a zinc-cbaltioyanid-aoyolieoh-polyether Complex 1st. BATH ORIGINAL 00 9818/1769